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The main aim of this article was to assess the atmospheric pollution with heavy metals due to copper mining Bučim near Radoviš, the Republic of Macedonia. The open pit and mine waste and flotation tailings are continually exposed to open air, which leads to winds carrying the fine particles into the atmosphere. Samples of attic dust were examined as historical archives of mine emissions, with the aim of elucidating the pathways of pollution. Dust was collected from the attics of 29 houses, built between 1920 and 1970. Nineteen elements (Ag, Al, As, Ba, Ca, Cd, Co, Cr, Cu, Li, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, and Zn) were analyzed by atomic emission spectrometry with inductively coupled plasma. The obtained values of the investigated elements in attic dust samples were statistically processed using nonparametric and parametric analysis. Factor analysis revealed three factors governing the source of individual chemical elements. Two of them grouping Ca, Li, Mg, Mn, and Sr (Factor 1) and Co, Cr, and Ni (Factor 2) can be characterized as geogenic. The third factor grouping As, Cu, and Pb is anthropogenic and mirrors dust fallout from mining operation and from flotation tailings. Maps of areal deposition were prepared for this group of elements, from which correlation of these anthropogenic born elements was confirmed.

BackgroundBioavailability of metals occurring in soil is the basic source of its accumulation in vegetables and herbs. The impact of soil pollution (due to urban and mining areas) on the food chain presents a challenge for many investigations. Availability of metals in a potentially polluted soil and their possible transfer and bioaccumulation in sorrel (Rumex acetosa), spinach (Spinacia oleracea) and common nettle (Urtica dioica), were examined.MethodsMicrowave digestion was applied for total digestion of the plant tissues, while on the soil samples open wet digestion with a mixture of acids was applied. Three extraction methods were implemented for the bioavailable metals in the soil. Atomic emission spectrometry with inductively coupled plasma was used for determination of the total contents of 21 elements.ResultsSignificant enrichments in agricultural soil for As, Pb and Zn (in urban area), Cd, Cu and Ni (in a copper mine area), compared with the respective values from European standards were detected. On the basis of three different extraction methods, higher availability was assumed for both lithogenic and anthropogenic elements. Translocation values >1 were obtained for As, Cd, Cu, Ni, Pb and Zn. Higher bioconcentrating value was obtained only for Cd, while the bioaccumulation values vary from 0.17 for Cd to 0.82 for Zn.ConclusionsThe potential availability of hazardous metals in urban and mining soils is examined using DTPA-TEA-CaCl2 (urban) and HCl (Cu-mines areas). Our results suggested that S. oleracea and R. acetosa have a phytostabilization potential for Cd, Cu, Ni and Pb, while U. dioica only for Cu. R. acetosa has a potential for phytoextraction of Cd in urban and copper polluted areas.

Distributions of a total of 21 elements were monitored in significantly lead-zinc polluted area using moss species (Hypnum cupressiforme and Camptothecium lutescens) used interchangeably, covering a denser sampling network. Interspecies comparison was conducted using Box-Cox transformed values, due to their skewed distribution. The median concentrations of trace elements in the both mosses examined decreased in the following order: Fe>Mn>Zn>Pb>Cu>Ni∼Cr∼As>Co>Cd>Hg. For almost all analyzed elements, H. cupressiforme revealed higher bio-accumulative abilities. For arsenic contents was obtained ER-value in favor of C. lutescens. The ER for the element contents according to the distance from the pollution source in selected areas was significantly enriched for the anthropogenic introduced elements As, Cd, Cu, Pb and Zn. After Box-Cox transformation of the content values, T was significantly different for As (4.82), Cd (3.84), Cu (2.95), Pb (4.38), and Zn (4.23). Multivariate factor analysis singled out four elemental associations: F1 (Al-Co-Cr-Fe-Li-Ni-V), F2 (Cd-Pb-Zn), F3 (Ca-Mg-Na-P) and F4 (Cu) with a total variance of 89%. Spatial distribution visualized the hazardously higher contents of "hot spots" of Cd > 1.30 mg/kg, Cu > 22 mg/kg, Pb > 130 mg/kg and Zn > 160 mg/kg. Therefore, main approach in moss biomonitoring should be based on data management of the element distribution by reducing the effect of extreme values (considering Box-Cox data transformation); the interspecies variation in sampling media does not deviate in relation to H. cupressiforme vs. C. lutescens.

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